高折射率聚硫氨酯的合成、结构与性能

doi:10.11949/0438-1157.20240654

摘要/Abstract

摘要：

聚硫氨酯作为一种高折射率光学树脂，具有优异的光学、热学和力学性能，被广泛应用于光电领域。研究了不同单体结构和单体官能团比对聚硫氨酯综合性能的影响，结果表明，聚硫氨酯的折射率和色散程度与其含硫量和芳环结构含量有较大的关系，调整官能团比可使高折射率聚硫氨酯的折射率从1.6848上升至1.6900。聚硫氨酯的热学性能和力学性能受到单体结构刚性、官能团度、交联网络均匀程度和反应程度多个方面影响。制备的大部分聚硫氨酯都可以很好地满足光学透镜、光学黏结剂等领域的要求。

关键词: 聚硫氨酯, 高折射率, 光学树脂, 反应, 合成, 聚合物

Abstract:

Polythiourethane, as a high refractive index optical resin, has excellent optical, thermal and mechanical properties and is widely used in the optoelectronic field. The effect of different monomer structures and monomer functional group ratios on the comprehensive performance of polythiourethane was studied. The results showed that the refractive index and dispersion degree of polythiourethane were closely related to their sulfur content and aromatic ring structure content. Adjusting the functional group ratio can increase the refractive index of high refractive index polythiourethane from 1.6848 to 1.6900. The thermal and mechanical properties of polythiourethane are influenced by various factors such as the rigidity of the monomer structure, the degree of functional groups, the uniformity of the cross-linking network, and the degree of reaction. Most of the prepared polythiourethane can be well applied in fields such as optical lenses and optical binders.

Key words: polythiourethane, high refractive index, optical resin, reaction, synthesis, polymers

中图分类号:

TQ 317.3

应昕, 杜淼, 潘鹏举, 单国荣. 高折射率聚硫氨酯的合成、结构与性能[J]. 化工学报, 2025, 76(2): 858-867.

Xin YING, Miao DU, Pengju PAN, Guorong SHAN. Synthesis, structure and properties of high refrective index polythiourethane[J]. CIESC Journal, 2025, 76(2): 858-867.

图/表 10

参考文献 33

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次数	31	174
比例	15%	85%

Property	PTU1	PTU2	PTU3	PTU4	PTU5	PTU6
composition	BES-XDI	BES-TDI	BES-MDI	PETMP-XDI	PETMP-MDI	BMMD-XDI
sulf content/%(mass)	29.48	30.66	25.16	14.80	12.94	25.87
refractive index（589 nm）	1.6560	1.6785	1.6862	1.5912	1.6261	1.6596
Abbe’s number	31.31	25.53	23.90	34.44	24.81	32.25
total transmittance/%	87.67±0.64	86.81±0.77	86.48±0.75	89.20±0.58	84.42±0.86	87.11±0.73
haze/%	0.22±0.08	4.1±0.13	0.06±0.02	2.07±0.09	18.78±0.20	0.71±0.11
λ_UV/nm	290	320	313	285	317	282
T_g(DSC)/℃	69.6	122.5	125.3	70.9	124.3	98.4
T_g(DMA)/℃	96.6	122.4	140.7	99.1	80.7/134.7	—
FWHM/℃	14.4	31.8	23.2	11.6	46.4/29.3	—
T_d5%/℃	280	262.1	268.6	290.6	279.6	282.9
T_dmax/℃	301.7	283.9	295.4	303.4	350.8	312.3
tensile strength/MPa	104.74±9.32	50.31±4.01	79.57±4.12	94.46±9.52	79.74±1.58	—
tensile strength at break/MPa	104.74±9.32	50.31±4.01	79.57±4.12	63.80±3.38	69.50±3.94	—
tensile strain at break/%	10.04±1.54	4.78±1.37	13.07+2.91	16.55±2.27	27.86±3.29	—
tensile yield strength/MPa	—	—	—	94.46±9.52	79.74±1.58	—
tensile strain at yield/%	—	—	—	9.92±0.49	11.61±0.45	—
pencil hardness	2H	2H	2H	2H	2H	3H
density/(g/cm³)	1.3633	1.3783	1.3417	1.3958	1.3846	1.4230
contact angle/(°)	94.87±2.28	94.02±5.34	92.35±3.47	94.52±1.18	77.24±1.69	83.95±0.69

Property	PTU1	PTU2	PTU3	PTU4	PTU5	PTU6
composition	BES-XDI	BES-TDI	BES-MDI	PETMP-XDI	PETMP-MDI	BMMD-XDI
sulf content/%(mass)	29.48	30.66	25.16	14.80	12.94	25.87
refractive index（589 nm）	1.6560	1.6785	1.6862	1.5912	1.6261	1.6596
Abbe’s number	31.31	25.53	23.90	34.44	24.81	32.25
total transmittance/%	87.67±0.64	86.81±0.77	86.48±0.75	89.20±0.58	84.42±0.86	87.11±0.73
haze/%	0.22±0.08	4.1±0.13	0.06±0.02	2.07±0.09	18.78±0.20	0.71±0.11
λ_UV/nm	290	320	313	285	317	282
T_g(DSC)/℃	69.6	122.5	125.3	70.9	124.3	98.4
T_g(DMA)/℃	96.6	122.4	140.7	99.1	80.7/134.7	—
FWHM/℃	14.4	31.8	23.2	11.6	46.4/29.3	—
T_d5%/℃	280	262.1	268.6	290.6	279.6	282.9
T_dmax/℃	301.7	283.9	295.4	303.4	350.8	312.3
tensile strength/MPa	104.74±9.32	50.31±4.01	79.57±4.12	94.46±9.52	79.74±1.58	—
tensile strength at break/MPa	104.74±9.32	50.31±4.01	79.57±4.12	63.80±3.38	69.50±3.94	—
tensile strain at break/%	10.04±1.54	4.78±1.37	13.07+2.91	16.55±2.27	27.86±3.29	—
tensile yield strength/MPa	—	—	—	94.46±9.52	79.74±1.58	—
tensile strain at yield/%	—	—	—	9.92±0.49	11.61±0.45	—
pencil hardness	2H	2H	2H	2H	2H	3H
density/(g/cm³)	1.3633	1.3783	1.3417	1.3958	1.3846	1.4230
contact angle/(°)	94.87±2.28	94.02±5.34	92.35±3.47	94.52±1.18	77.24±1.69	83.95±0.69

Property	1	2	3	4	5	6	7	8	9
—SH/—NCO	0.90	0.95	1.00	1.05	1.10	1.20	1.30	1.40	1.50
refractive index（589 nm）	1.6848	1.6859	1.6862	1.6871	1.6880	1.6886	1.6895	1.6898	1.6900
Abbe’s number	23.48	23.48	23.90	23.95	24.00	24.35	24.05	24.41	24.46
total transmittance/%	86.62±0.83	86.50±0.69	86.48±0.75	86.48±0.62	86.35±0.87	86.34±0.93	86.50±0.76	86.20±0.68	86.36±0.91
Haze/%	0.09±0.02	0.17±0.04	0.06±0.04	0.04±0.03	0.16±0.05	0.50±0.08	0.59±0.06	0.47±0.09	1.57±0.10
λ_UV/nm	313	313	313	312	312	311	311	311	311
T_g(DSC)/℃	131.3	127.8	125.3	119.9	119.4	101.1	98.0	89.7	69.4
T_g(DMA)/℃	153.3	147.2	139.5	131.9	129.1	116.6	107.2	102.3	89.7
FWHM/℃	33.5	38.7	36.0	30.0	28.5	23.3	19.7	17.5	19.1
T_d5%/℃	266.3	268.6	268.6	268.0	271.8	270.5	269.2	269.0	266.2
T_dmax/℃	290.1	292.5	295.4	293.6	297.1	290.1	290.9	287.6	286.0
tensile strength/MPa	60.31±3.25	72.06±3.42	79.57±4.12	77.73±5.18	73.28±4.72	72.12±2.21	68.69±3.35	67.48±3.72	37.48±3.80
tensile strain at break/%	7.45±1.66	8.37±1.58	13.07±2.91	15.7±3.13	17.42±2.68	16.84±3.89	11.58±1.73	6.89±1.76	4.02±1.30
pencil hardness	2H	2H	2H	2H	2H	2H	H	H	HB
density/(g/cm³)	1.3356	1.3392	1.3417	1.3463	1.3497	1.3573	1.3625	1.3686	1.3715
contact angle/(°)	91.60±2.15	100.03±1.76	92.35±3.47	95.34±1.38	98.17±1.24	93.94±2.91	90.95±1.79	101.39±1.21	97.30±1.41

Property	1	2	3	4	5	6	7	8	9
—SH/—NCO	0.90	0.95	1.00	1.05	1.10	1.20	1.30	1.40	1.50
refractive index（589 nm）	1.6848	1.6859	1.6862	1.6871	1.6880	1.6886	1.6895	1.6898	1.6900
Abbe’s number	23.48	23.48	23.90	23.95	24.00	24.35	24.05	24.41	24.46
total transmittance/%	86.62±0.83	86.50±0.69	86.48±0.75	86.48±0.62	86.35±0.87	86.34±0.93	86.50±0.76	86.20±0.68	86.36±0.91
Haze/%	0.09±0.02	0.17±0.04	0.06±0.04	0.04±0.03	0.16±0.05	0.50±0.08	0.59±0.06	0.47±0.09	1.57±0.10
λ_UV/nm	313	313	313	312	312	311	311	311	311
T_g(DSC)/℃	131.3	127.8	125.3	119.9	119.4	101.1	98.0	89.7	69.4
T_g(DMA)/℃	153.3	147.2	139.5	131.9	129.1	116.6	107.2	102.3	89.7
FWHM/℃	33.5	38.7	36.0	30.0	28.5	23.3	19.7	17.5	19.1
T_d5%/℃	266.3	268.6	268.6	268.0	271.8	270.5	269.2	269.0	266.2
T_dmax/℃	290.1	292.5	295.4	293.6	297.1	290.1	290.9	287.6	286.0
tensile strength/MPa	60.31±3.25	72.06±3.42	79.57±4.12	77.73±5.18	73.28±4.72	72.12±2.21	68.69±3.35	67.48±3.72	37.48±3.80
tensile strain at break/%	7.45±1.66	8.37±1.58	13.07±2.91	15.7±3.13	17.42±2.68	16.84±3.89	11.58±1.73	6.89±1.76	4.02±1.30
pencil hardness	2H	2H	2H	2H	2H	2H	H	H	HB
density/(g/cm³)	1.3356	1.3392	1.3417	1.3463	1.3497	1.3573	1.3625	1.3686	1.3715
contact angle/(°)	91.60±2.15	100.03±1.76	92.35±3.47	95.34±1.38	98.17±1.24	93.94±2.91	90.95±1.79	101.39±1.21	97.30±1.41

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